Process for purification of crystals



Sept, 30, M58

I R. W. THOMAS PROCESS FOR PURIFICATION OF CRYSTALS Filed March 17, 1955 INVENTOR. R. W. THOMAS W M y ATTORNEYS monoj 51.52

P030011 ET :w JOE-r200 wJU U Unite Stas PROCESS FUR PURIFICATKON or CRYSTALS Application Friar-ch 17, 1955, Serial No. 494,366

11 Claims. (Cl. 260674) This invention relates to a process for the resolution of mixtures by crystallization. In one aspect, it relates to an improved apparatus for crystal purification.

Purification by means of fractional crystallization has been known for a number of years. Schmidt Re. 23,810 (1954) discloses a process and apparatus for purifying crystals, which process involves moving a mixture of crystals and adhering liquid through a liquid removal zone, a reflux Zone and a melting zone, removing liquid in said liquid removal zone, melting crystals in said melting zone, withdrawing part of the melt as product and forcing another part of the melt in a direction countercurrent to the movement of crystals in said reflux zone. This process is generally applicable to the separation of at least one pure component from any mixture which is resolvable into its components by fractional crystallization. For example, the process can be used for the concentration of fruit juices, vegetable juices, and other. materials which comprise aqueous solutions which can be concentrated by the formation and removal of ice crystals. The process is also of great value in the resolution of non-aqueous mixtures, an example of such an application being the separation of para-xylene from a mixture thereof with the other xylene isomers and ethyl benzene.

The present invention provides a process and an apparatus for eifecting a separation of the type described at .higher throughput rates, improved stability and ease of operation, and improved heat distribution. In addition, products of high purity are obtainable over long periods of operation.

According to this invention, in a process wherein solids t are countercurrently contacted with a liquid in a purification zone, the solids are supplied continuously to said zone while the liquid is supplied intermittently.

Further, according to this invention, there is provided, in a process which comprises moving a mass of solids, together with adhering liquid, through a liquid removal zone, then through a reflux zone and finally through a melting zone, withdrawing liquid in said liquid removal zone, melting at least part of said solids in said melting zone, removing part of the melt from said melting zone and forcing another part of said melt into said reflux zone in a direction countercurrent to the movement of solids therethrough, the improvement which comprises contacting the solids in said zones with an intermittent flow of reflux liquid simultaneously with the propulsion of said solids through said zones.

Further in accordance with this invention, there is provided, in an apparatus comprising a purification chamber, liquid-solid separation means in said chamber, melting means positioned in one end of said chamber, means for moving solids to said separation means and thence toward said melting means, means for removing melt from said chamber, and means for removing liquid from said separation means, the improvement which comprises means for producing an intermittent fluid-flow in a di+ atent O 2,854,494 Patented Sept. 30, 1958 2 rection from said melting means toward said liquidsolid separation means.

According to one embodiment of the invention, a mass of crystals to be purified, together with accompanying liquid, is passed through a purification chamber containing a filter which is integral with the wall of said chamber and positioned at an intermediate part thereof, then through a reflux zone toward a heating mean positioned in one end of the chamber, which heating means melts the crystals which arrive in the vicinity thereof. The melt is withdrawn in part as purified product, and forced, in part, into the reflux zone toward the filter, and a pulsating back pressure is applied to the contents of the 'purification chamber by means of a reciprocating piston positioned in a cylinder which is in open communication with said chamber at the end in which said heating means is positioned. The reciprocating motion of the piston can be produced by means which are well understood in the art, for example, by a mechanical crank attached to a motor or by an electric oscillator. The back pressure is sufficient to produce a counterflow of liquid relative to the movement of the crystals. Thus, according to this invention, when the solids are supplied steadily during a given period of time to the purification zone, the reflux or other purifying liquid is moved intermittently in the opposite direction, i. e., countercurrently with respect to the solids.

The drawing illustrates three embodiments of this invention.

Figure 1 illustrates one embodiment of this invention wherein pressure pulsations are produced by a reciproeating piston.

Figure 2 illustrates a modification of the apparatus of Figure 1.

Figure 3 illustrates a further modification wherein a flexible diaphragm is utilized.

Corresponding numerals indicate corresponding parts in each of the three figures.

The apparatus of Figure 1 comprises freezing or crystallizing means A, a filtering means B, a reflux zone C, a melting section D, and a pulsation-producing device E.

A feed mixture comprising two or more components, one of which is separable from the mixture by crystallization, enters the apparatus through inlet 2 and is forced by means of pump 3 into the chilling section A-of the main purification column. The purification apparatus is composed of a cylindrical shell 4, to which is attached a cooling section which comprises a cylindrical shell 5. The shells 5 and 5 can be constructed of ordinary metal pipe and can be welded together at any desired angle, as indicated in the drawing; or they can be connected by flanges or by threads. Alternatively, they can be one single length of pipe which can be built in the form of an elbow at any desired angle. The particular angle shown in the drawing can vary within a very broad range or the entire apparatus can be straight.

' The purification apparatus is closed by means of end members '6 and 7, which can be of any suitable form known in the art. Crystallization section A comprises, in addition to shell 5, a cooling jacket 8 having inlet 9 and outlet 10. Positioned within the crystallization section is an agitating or scraping means 11, which is designed to prevent the accumulation of solid material on the heat exchange surface. Scrapers 11 are suitablyconstructed of strips of metal or other suitable materials known in the art. They can be fabricated in the form of a helix, as indicated in the drawing, or can be straight. Any suitable number of scrapers 11 can be provided. They are mounted on a rotatable shaft 12 by means of members 13. Shaft 12 is axially positioned in shell 5 and is connected to any suitable source of power for rotat- 'of any desired type known in the art.

3 ing the scrapers, such power source not being shown in the drawing. Shaft 12 is suitably sealed in end member 6 by means of a packing gland of any desired type known in the art. Suitable cooling of the feed which enters shell can be provided byaddinga coolant through inlet 9 and withdrawing thecoolant through outlet 10. Suflicient cooling in section A is" provided so ably positioned within the purification column at a point by thermocouple 29 to an air pressure which is utilized that a predetermined amount of solid crystals is produced,-as subsequently discussed herein. The resulting crystal mass passes through purification chamber 4. and into filter section B. 7

As a general rule, the feed pump 3 is generally suitable for forcing the crystal mixture through the purifica-' tion column. However, othermeans for propelling the mixture through the purification zone can beprovided, as shown in the cited Schmidt reissue patent. Where such means, for example, a piston, is provided, it can be positioned upstream from section A or intermediate the chilling section A'and purification section 4, or other suitable arrangements can be provided by those skilled in the art.

Filtration section B comprises a suitable filter medium 14 and an external shell 15, the latter being provided with anoutlet pipe 16 for filtrate. Filter medium 14 can be For example, it can comprise a metallic screen, a sintered perforate metal member or a perforate metal member supporting a filter cloth. In any event, it is desirable that the filter member 14 be positioned integrally with respect to the shell 4.

Filtrate produced in filter zone B is removed from the system through outlet 16.

' The remaining crystal mass passes through reflux zone C. whereinit is countercurrently contacted with liquid reflux produced as subsequently described.

As the crystal mass approaches heater 17 in meltlng section D, thecrystals are melted. Heater 17 can be in -the formof an electrical heater or a heat transfer coil through which a suitably heated fluid is pumped. Part of the melt produced by heater 17 is withdrawn through outlet pipe 18 as a purified product of the process. The remainder of the melt is forced back through reflux zone C to form reflux which effects crystal purification, the

resultin liquid being drawn off through outlet 16, to-

gether with the filtrate. Although an internalheater 17 is shown, an external heater, for example, a heating jacket encompassing section D and provided with means for circulating a heating fluid therethrough, can be used, if desired.

The pulsation-producing member E comprises a cylinder 19 which is suitably attached to closure member 7 as, for example, by welding, and closure means 20, together with a reciprocatable piston 21. Piston 21 is suitably sealed in cylinder 19, for example, by means of rings 22, to prevent the leakage of melt from the purification. Reciprocationof piston 21 is produced, for example, by an electric motor 23, a belt 24, a crank means 25, and connecting rods 26, which can be sealed in closure member 20 by means of a packing gland. 'An outlet 27 is provided in closure member 20 to facilitate the reciprocation of piston 21 and can be connected to means, notshown, for recovery of any material which might escape from column 4 in case of failure of rings 22.

While the crystal mass is being'advanced from chilling section A through filtration-section B, reflux section C, and melting section I), piston 21 is reciprocated at a suitable rate, which is subsequently discussed herein, so that a pulsating pressure is exerted on the melt reflux which is intermittently forced ack, countercurrently with respect to the crystal mass, through reflux zone C. In melt outlet 18 is positioned a check valve 28 to prevent the back flow 0f withdrawn melt into the crystal purification column. A temperature recorder-controller, designated in the drawto open or close valve 30. The temperature recordercontroller is suitably so adjusted that an undesirably rapid advance of crystals through reflux zone C results in a predetermined low temperature which is measured by thermocouple 29, which operates through the temperature recorder-controller to throttle valve 30 and decrease the rate of withdrawal of melt. An undesirably slow advance of crystals through the purification column produces the opposite effect. The described combination of apparatus and the method for controlling melt withdrawal rate is disclosed and claimed in copending application Serial No. 514,499, filed June 10, 1955, by J. D. Ratje.

Also shown in the drawing is a cycle control device 31, of known design, which is operatively'connected with motor 23 so that an electrical pulse is produced in synchronism with piston 21. The cycle control 31 can be so adjusted that, on the compression stroke of piston 21, an otherwise closed solenoid valve 32 is opened, resulting in the removal of filtrate from the purification column only on the compression stroke of piston 21. Also provided, to aid in accomplishing this effect, is check valve 33 in filtrate withdrawal line 16. A similar arrangement can be effected in connection with the withdrawal of melt through outlet 18. However, it is preferred, in such a case, that the melt withdrawal cease during the compression strokeof the piston. Means for producing this result are not shown in the drawing. Cycle control means 31 can, for example, be operatively connected to crank 25 or connecting rods 26. It can include an electrical make-and-break device, such devices being well known in the art.

It has been found that although the described synchronism of withdrawal with the compression stroke of the piston 21 produces satisfactory results, it is not necessary for obtaining the benefits of this invention. A suitable, and often preferred, arrangement is to utilize bypass 34, solenoid valve 32 and/or check valve 33 being closed and by-passed. In this mode of operation, it is desirable to utilize a predetermined back-pressure on the liquid being withdrawn through outlet 16. This backpressure is to be distinguished from that intermittently applied by the piston within the column. The filtrate or mother liquor back-pressure is an external back-pressure and can be constant; it need not be intermittent. For the purpose of controlling filtrate back-pressure, a pressure indicator-controller designated as PIC in line 16, can be utilized. This instrument is of a type well known in the art and converts a back-pressure in the liquid withdrawal line 16 to an air pressure, which suitably throttles motor valve 35 to maintain a desired back-pressure in line 16. A similar instrument arrangement can be utilized ingas TRC, is provided and is connected to asuitable in connection with valve 36 in melt withdrawal line 18. The foregoing external back-pressure control is disclosed and claimed in copending application Serial No. 514,499, filed June 10, 1955, by J. D. Ratje.

It is also within the scope of this invention to withdraw melt through outlet 18 at a constant rate, utilizing metering equipment known in the art.

In the arrangement shown in Figure 2, the cylinder 20 is spaced from the cylinder 4 and is connected therewith by means of an open conduit 40.

In Figure 3, the piston 20 is separated from the contents of thepurification column by means of an intermediate fluid which is supplied through valved conduit 50. The piston acts-directly upon the intermediate fluid and, in turn,-produces a pulsation of a flexible diaphragm 51, which is suitably sealed within a chamber 52. The intermediate fluid can be any noneorros'ive fluid. It is :preferabl'y'a liquid, such as a vegetable oil, which is inert with respect to the materials being separated in column 4 and which is readily a" mineral lubricating oil or and chamber 52. Alternatively, diaphragm 51 can be actuated pneumatically, or by means of a direct, reciproeating, mechanical linkage attached to the"diaphragm, or electrically, as by means of a solenoid, or by any other desiredmeans for producing a reciprocating fiex-ure. Also, the diaphragm can be placed in end'member 7, e. g., concentrically therewith, or 'can replaceend member 7, the melt being withdrawn from a side outlet. Further, the diaphragm 'can'be sonically or supersonically, or even subsonically, vibrated. 1

Although purification chamber 4 is shown positioned horizontally, it can beoperated in other positions; for example, it can be maintained in a vertical 'position'with cylinder and piston 21 at the top. This arrangement utilizes gravity as an aid to the flow of reflux.

Although, as stated, an additional piston can be'utilized for propelling the crystals through'thecrystallization column, I have found that sucha' device is ordinarily unnecessary,'suitable propulsion beingprovided by a feed pump 3, especially when the purification column is horizontal or nearly horizontal. scope of this invention to utilize two pistons, one to propel the crystals through the purification column and the other to produce'a pulsating reflux stream. Thelatter piston is ordinarily operated at a frequency greater than that of the former, so that during a sustained movement of solids within a given time interval, an intermittent counterflow of reflux liquid is simultaneously effected.

A- further suitable modification of the invention can be provided by positioning in reflux zone C a heat-transfer grid of the type shown in the copending application of T. A. Tarr, Serial No. 477,099, filed December 22, 1954. It has been found that certain ranges of frequency of pulsation of the back-pressure applied according to this invention produces results superior to certain other ranges of frequency. In the separation of para-xylene from its isomers, improved results are obtainable at a frequency as low as 15 pulsations per minute or as high as 200 pulsations per minute. However, outstanding results are obtained at from 50 to 165 pulsations per minute. Highly superior results are obtained in the range from 125 to 1 50 pulsations per minute. It has been found that within the preferred range the" operation of the purification column is greatly stabilized and the movement of material It is, however, within the,

therethrough is greatly facilitated. Thus the attainment.

and maintenance of phase equilibrium, as indicated by temperature gradients within the column, is greatly facilitated by the use of pulsating back-pressure and reflux flow according to this invention. As regards production of a high-purity product consistently over an extended period of time, a critical lower limit of frequency exists at about 50 pulsations per minute in the purification of para-xylene. Broadly, however, the invention is not so limited.

The dimensions of the cylinder and piston used to pro duce the back-pressure pulsation can vary over a rather wide range. It has been found that when a purification column 6 inches in diameter is used in conjunction with a two inch diameter piston for the separation of paraxylene from its isomers, the piston stroke can be in the range /2 to 2 /2 inches, preferably /1 to 2 inches, and it has been found that a 1-inch stroke appears to produce optimum results in terms of ease and stability of opera tion. Optimum dimensions in any particular case can readily be determined by trial by those skilled in the art. It is to be understood that the dimensions, configurations, and frequencies stated above are not necessarily optimum for every material to be purified.

As previouslydescribed, it has been found desirable to maintain a predetermined back-pressure on the filtrate Withdrawal conduit. It appears that, by controlling the back-pressure, the proportion of solids in the feed'to'the purification column is, in turn, controlled. A backpressure in the range 70 to p. s. i. has been found highly desirable in thepurification of para-xylene. This F feature is; disclosed and claimedin copending application Serial No. 514,499, filed June 10, 1955, by -J. D. Ratje.

' It is often desirable to control the relative proportions of solid and liquid in the feed which is introduced into the purification column. It is generally desiredthat this proportionbe' such that the mixture has sufiicient of the properties of a liquid or slurryto allow transfer of the mixture by pumping. On the other hand, it is generally desirable to have sufiicient solids present so that themixture has some apparent compressibility; otherwise a waterhammer effect issornetimes produced by the action of the means providedto produce a pulsating back-pressure. The optimum ratio of solids to liquid depends onthe particular-materials to be separated, on crystal size, and on other factors and can readily be determined in any particularcase' by routine test. As a general rule, the solids content of the mixture fed from the chiller into the purification column is within the range 20 to 36 weight percent, and preferably 25 to 30 weight percent. However, solids contents outside the stated ranges can be used.

Although the back-pressure within the purification column is preferably applied by the piston or other pulsator in a'regular or periodic or pulsating manner, an irregular or non-periodic increase of back-pressure is within the scope of the invention. It is also within the scope of the invention to operate with a compression stroke of the pulsator which is of longer duration than the return stroke or vice versa. This can be effected by suitable mechanical lost-motion devices connectedwith the means used to connect the piston or other pulsator to the source of motive power. Such devices are wellknown in the art. Also, electrical, pneumatic or hydraulic actuation of the pulsating mechanism can be utilized in place of purely mechanical actuation.

It is also within the scope ofthe invention to utilize two or more purification units, of the type described, in series. This type of operation is of particular value when the raw material from which it is desired to concentrate a particular component is relatively dilute with respect to that component. For example, in a hydrocarbon mixture containing approximately 18 weight percent para-xylene together with other xylenes and ethylbenzene, the raw mixture can be passed through a purification unit of the type described in Figure 1 to produce a concentrate containing, for example, 60 weight percent para-xylene, which concentrate can then be passed, after at least partial melting, if desired, to a second unit of the type shown in Figure 1. The first unit can be operated with or without the use of pulsating back-pressure, a pulsating backpressure being used in the second unit. More than two such units can be used in series. Alternatively, the preliminary concentration can be accomplished by crystallization and subsequent filtration, although this method is not necessarily equivalent to the use of two or more pulsator-equipped units in series as previously described.

The use of parallel arrangements of two or more units of the type described is also within the scope of the invention. Combinations of series and parallel arrangements are also feasible.

From the foregoing, it Will be seen that, according to this invention, a pressure in the melting zone of an apparatus of the type described is intermittently produced, which pressure is greater than that at the locus of filtrate withdrawal. An intermittent reflux flow is thus created simultaneously with the propulsion of solids through the apparatus. I

In the following examples, the operation of a column Durpositions,

Compose its product seamen w anew .nnuw nuwm Notes percent p-xylens HHUHMMMMMMMMMMW 4 Average, pressures tion could be varied Thus, when the Stream com wwmwwmwwwwwmmww iproca A Commercially available n opposite to that of er. Representative data lated' mol slurry qnality,wt;

nt Feed ML p xylene a meanness o p we wwwmawaeew anaaaaaenneea moi percent 8 ',=.--said:.linkage being such that the 'The controller .was operated to raise c. an. Calcu- Product :ML

Stream compositions,

wwmwwwwwwmmww min.

weitrar ummmn mmmmm Rates, G. an.

Product ML Feed Mri MMMMMMMMMMM ton stroke and the rate of rec A feed comprising "weight percent para-xylene, the

runs piston 0 in. y a

min.

:a rotary electric m pis ' over. a rather broad range.

temperature recorder-controller was provided for measur- 8 ing the. temperature at the electri l heater within the column and controlling the product withdrawal rate, in

response 'to saidtemperature, by control of a valve in the -'melt withdrawallirie.

keepthedownstr'cam" end of the crystal mass in contact stream from the heater,=the withdrawal rate was automatically increased, and'if crystals moved past the heater,

the withdrawal rate was automatically decreased :ing some of the runs,.a solenoid valve positioned in the piston by means of a'microswitch actuated by a cam attachcd to the cylinder connecting rod;

piston was moving in adir crystal movement, the solenoidvalve in the filtrate e stroke of thelpiston, the solenoid valve closed, and no filtrate was removed.

impurities being chiefly orthoand meta-xylene and ethyl benzene, was supplied to the chill obtained under diiferent conditions are shown in the following tables. 1

Host- Pulse piston Stroke, Cycles,

Table l Table II ornna'rme para Gauges were snubbed; hence, they tend record average pressures.

outlet umn 1 net,

Prodj Thepurification column Pressures, p. s. i. g.

(J ginger Chiller 01- Prodwatts snore RESULTS OF TESTS OF CONTROL DEVICES Pressures, p. s. i. g.

Chiller Heater secoutlet ML uet tion EXAMlLlZ I Wall liquor 5- 7 68. 73 5- ([2 67-70 120-130 4- 6 70-74 -157 3- 5 70-74 1 to +3 69-71 1 to 4 67-73 7 67-76 6- 7 ,66-71 8-10 .69-70 10-11 67-72 [lrinch diameter, horizontal, pulsed column with 60 percent p-xylene teed-fractional a'ystalli'zation] Wall liquor [fi'inch diameter, horizontal, pulsed column with 60 percent p-xylene teed-traction crystallization] Temperatures, "F.

Chiller outlet gressures cycle with the pulse piston cycle.

e table.

Temperature, 1".

Chiller outlet Thepurificationi-unit utilized in these examples was of the type illustrated in Figure 1. was constructed of flangedsteel pipe 6 inches 111 diameter and approximately 2% feet in length, the column being 10 'withthe electrical heater. Thus, if crystals melted upof flangesat an angle of ,8 40f with,the h,orizonta 1 The chiller was providcdwith a; jacket through which coolant l5 filtrate withdrawalline was synchronized with the 2-inch was circulated, Within thechi-llerwas a scraper of the which was connected a 2-inch diameter cylinder provided with a piston, as illustrated in Figure 1; The 2-inch piston was driven by means of a mechanical linkage with Period oioperation,

in accordance with this invention is;illustrated,:;in con- ;nection with the separation and purification of para-xylene from a mixture of para-xylene with' ortho-. and. metaxylenes and ethyl benzene.. I K 4 horizontally positioned. Connected to one end of the column was a .6 inch diameter scraped-surface chiller, 20 feet; in length andconnected to the column bymeans type illustrated inv Figurel. Adjacent the end of ,the column to which the chilleljwasconnected was a wall filter 10 inches long, with a filtratewithdrawal conduit. In the opposite endof the purification column was posi- 20 opened so that filtrate was withdrawn; on the opposi -tioned an electrical heaterapproximatelyfi to"8 inches from the product outletend; A product withdrawal conduit was connected to themelting end of the column. This end of the columnwas provided with a flange to 1 Column are shown in t ML=mother liquor.

Duration oi run, hr.

(I) Chiller feed surge pot was bypassed. (b) The mother liquor solenoid valve, used on cycle control in phase with pi: ton motion, was bypassed. The check valve on the mother liquor line from the column was bypassed. A back-pressureeontroland motor valve were used in place of an integral back-pressure regulator usedin other runs.

Table III OPERATING DATA [ti-inch. diameter, horizontal, pulsed column 60 percent p-xylene feed-fractional crystallization] Temperatures, F. Pressures, p. s. i. g. Pulse piston Rates, G. P. H. Stream composition, mol percent p-xylene Duratign of Heat, watts run, r.

Chiller Wall Heater Chiller ML Product Stroke, Cycles, Product ML Feed ML Composite outlet l quor section outlet in. min. product -2 2. 4 67-70 90 85 90 2, 645 79 140 12. 8-13. 3 41-45 58 46 98. 4-99. 0 2-5 4-6 61-70 90 90 90 2, 130-2, 645 140 9. 7-13. 8 23-50 58 47 91. 5-98. 5 0-2, 1-6 67-82 80 80 90 2, 130-2, 810 140 11. 4-15. 1 28-40 59 45 96. 2-97. 6 1-3 2-4 80-86 80 80 85 2, 750-2, 945 140 12. 6-14. 8 32-37 60 44 98. 9-99. 1 2 4 68-70 85 85 90 995 94 140 14. 7-15. 0 60 44-48 94. 1-98. 9 1-5 2-5 66-79 95 90 95 2, 765 1% 140 12. 9-24. 8 30-38 60 44 98. 1-98. 6 l-3 3-5 66-78 100 80 105 2, 575 1% 140 11. 4-14. 9 31-89 60 44 98. 0-99. 5 3-4 5. 7 72-82 105 85 105 2, 590 94 160 10. 2-12. 9 38-44 60 45 98. 0-99. 5 3-4 6-25 76-82 105 90 115 2, 590 A 160 11.6-13.0 -44 60 98. 0-98. 9 l-2 1-4 74-85 95 80 95 2, 390 1% 128 8. 9-11. 9 27-31 61 44 98. 1-98. 6 1-2 4-5 73-79 105 90 106 2, 440 1% 128 10. 6-12. 7 32-34 61 45 98. 0-98. 5 1 2-5 73-77 105 85 110 2, 160 1% 128 9. 5-10. 8 28-32 45 98. 4-98. 9 1-2 2-5 56-61 105 90 105 1, 880 Z5 128 8. 8-11. 1 27-31 60 45 98. 0-99. 1

The foregoing data show that good results were obpressure reached 120 p. s. 1. The data for wlnch no tained at a pulsation frequency of approximately 125 to 160 pulsations per minute. A frequency of 140 pulsations per minute appeared to be optimum. It will be noted that throughput rates of the order of 35 to 36 gallons per hour were readily maintainable with the 6- inch diameter column. This is equal to rates which are consistently attained in an 8-inch diameter column in commercial operation without the pulsation feature of 30 this invention. Thus, it is clear that thisinvention provides high throughputs, stable operation and high product purity.

times are given represent individual readings in runs varying in length from several hours to several days.

EXAMPLE III This example illustrates the effect of pulsation frequency on the purification of para-xylene according to this invention.

The apparatus utilized in this example was similar to that utilized in the preceding example but had the following difierences:

(1) The purification column was vertically positioned EXAMPLE II and had a length of approximately 26 inches and a di- 35 ameter of approximately 5% inches. The filter was 7 d In a systen 9 s lf? ig u l f f inches long and provided 46 square inches of filtration ata were 0 s Owmg e res ts varymg Ce am area. The purification column was connected, by means other process variables.

Table IV [ti-inch diameter, horizontal, pulsed column-=60 percent p-xylene feeCL] Temperature, F. Pressure, p. s. i. g. Flow rates, G. P. H. Stream com-positions,

mol percent p-xylene Dura- Heat, Rate, Stroke, tion of Chiller Column watts cycles, in. run, hr. Chiller Wall Heater min. (3

outlet liquor section Product ML Feed ML posite' In Out ML Prodproduct 0-1 73-81 90 85 150 3, 121% 160 5 16 12.8-18.4 30-46 57 41-44 94 7-96. 2 4-5 66-74 110 35 175 2, 2 6% 160 114 11. 5-14. 1 34-43 56 43- 44 94. 7-97 1-3 69-72 115 110 100 2: 590 140 1 12. 9-13. 5 33-40 56 43-44 95. 0-99. 2 1 to +1 61-68 120 120 80 115 2,590 140 1 11.8-15.8 30-49 57 41-43 99.3-99.9 7-9 63-69 115 120 100 120 3 032 140 1 16. 0-16 9 54-60 60 46-47 98.2-98.7 7.5 34 4-6 60-71 105 115 so 120 4; 150 140 1 20.4-21.9 58-62 60 46-47 95.5-98.9 4 5 56 105 120 80 120 4,150 140 1 23.2 65.2 60 47 96.1 4 6 67 105 125 50 115 4,150 140 1 19.7 57.3 60 46 98.4 3 3 s0 95 105 80 120 4, 150 140 1 19.0 51.1 60 46 99.1 4 6 97 105 120 80 110 4,150 140 1 17.6 52.4 60 46 98.0 3 4 71 110 so 105 2,610 140 1 13.0 36.9 59 44 99.3 3 3 58 110 100 so 125 2, 610 140 1 3 13.8 39. 8 59 45 99.3 4 4 53 110 100 80 110 2,610 140 1 4 15.6 45. 0 59 45 98.0 4 4 75 100 90 75 2,610 140 1 12. 1 32. 7 60 42 99. 5 4 4 74 110 90 2, 610 140 1 12.6 31. 3 60 42 99.6 4 5 74 110 100 100 95 2,610 140 1 13. 0 33. 7 60 45 '99. 0 5 5 73 120 110 130 2,610 140 1 13.2 33.3 60 46 99.1 4 5 75 120 115 2, 610 1 12. 7 30. 8 60 45 98. 6 4 5 70 125 125 120 130 2, 610 140 1 12. 8 35. 4 60 46 92. 7 4 4 76 125 120 105 125 2, 610 140 1 12.4 33.8 60 45 99. 5 4 5 73 110 100 so 100 2, 610 140 1 12. 5 34.6 60 45 99. 3

System pressures cycle at the same rate as the pulse unit. Gauges are snubbed and tend to indicate average pressures.

1 Maximum heating rate with installed heater. 8 Estimated.

The foregoing data show that a back-pressure on the filtrate withdrawal line in the range 75 to 120 p. s. i. is highly desirable in the described purification of paraof'an elbow, with a chiller, of the type utilized in the previous examples, the chiller being positioned at a slight angle with respect to the horizontal so that the xylene. The product purity decreased when the back- 75 outlet end connected to the purification column was lower 2,804,494 m 11 12 than the feed inlet end. This apparatus provided-a pared. Table V shows results obtained without the use gravity reflux when the pulsating piston was not used., of the pulsating piston according to this invention. Table Thus, the performance of the column with and without 'VI shows the results obtained when the piston was utilized the pulsating piston, according to this invention, was comat various pulsation frequencies.

Table V TYPICAL OPERATING DATA [6-inch diameter inverted column (pulsed-piston not in operation) 60 percent p-xylene feed.)

Temperatures, F. Pressures, p. s. 1. 3. Rates, 5. p. h. Stream composition,

7 percent p-xylene Heat, Chiller Column watts Nous Col. Prod- Prod- Col. teed ML base uct ML Feed ML not In Out ML Prodnot 12 105 95 25 25 960 5. 8 17. 3 60 49 81. 8 13 130 92 26 25 1, 500 8. 7 36.0 57 51 81.8 V 8 170 88 26 '27 2,180 11.0 35.4 58 51 83.0 13 178 92 27 26 2, 310 9. 6' 19.4 58 51 90.0 14 190 95 33 26 26 3, 190 13. 1 21.2 60 48 783 16 198 95 37 25 26 3, 390 13. 5 28. 9 59 50 79.5 15 165 55 29 25 26 2,740 10.8 23.0 59 50 v 78.2 14 178 165 35 -25 p 25 2,' 760 11. 3 22. 8 59 49 80. (0 182 195 42 25. 25 2, 760 11.3 24, 9 59 46 '81. 8 14 168 95 15 5 8. 2, 840 12. 8 32. 4 59 49 79.0 i 17 164 98 45 35 35 2,840 15.0 34.8 59 49 78.0 d 15 163 1(1) 65 65 65 2, 860 13.4 16.9 59 50 76. 2 i 15 105 95 40 20. 23 2, 740 19.9 34. 6 59 49 79.0 13 149 100 34 22 2, 740 20. 7 23. 6 60 49 78. 5 15 195 100 20 20' 2, 760 11. 1' 15. 2 (D 49 79. 5

A study of the eflect of throughput on product purity. 'lhe 3,390 watt heating rate was the lull capacity of the installed heaters. A study of the effect of iced pressure on operating characteristics. A study of the effect of product-line back-pressure on operating characteristics. -A study of the eflect of eater zone temperature on operating characteristics.

Table VI OPERATING DATA [6-inch diameter, inverted, pulsed column-60 percent p-xylene feed] Temperature, F. Pressures, p. s i. g. Pulse piston Rates, g. p. h. Stream compositions,

percent p-xylcne Chiller Column Heat, w Not 001. 00]. watts Speed, Stroke, teed ML base cycles] in. Product ML Feed ML Product Comp.

In Out ML Prodmin. product not ,7 v p Product rate control based on heater zone temperature used in all following tests 18 127 74 73 75 75 2, 110 16 2 11. 6 33. 6 59 51 85. 5 79. 5 19 151 68 68 68 67 2, 110 16 2 10. 2 42. 3 59 52 88 0 88. 0 17-18 143-146 60 60 70 73 2, 110 16 2 9. 2-9. 7 36. 0-37. 4 59 52 8). 5 89. 5 60 60 65 70 2, 110 16 2 9. 2 34. 2 58 54 93. 4 88. 0 18 113-123 55-59 50-55 55-57 55-65 2, 110 16 2 0. 9-9. 1 48. 9-74. 0 59 54 79. 7 79. 7-62.0 5 5 75 1, 680 16 2 10. 6 42. 5 57 52 92. 0 91. 0 15-17 116-130 140-145 135-140 135-145 125 2, 180 32 2 11. 1-14. 3 21. 9-26. 8 59 59-53 785-81. 7 79. 5-U.5 15 1 140 2, 310 32 2 8. 5 39. 0 60 52 97. 2 94. 4 15-16 93-118 130-135 125-135 127-135 60-68 2, 610 32 2 7. 2-12.2 24.6-32.0 60 52-54 86. 087.5 76.0- 85. 5 143 1 2, 120 32 2 7. 9 36. 4 60 97. 1 97. 1 14 138 105 105 102 23 2, 120 32 2 7. 1 26. 8 60 50 98. 5 96. 9 138-159 120-130 115-130 35-135 90-110 2,140 32 2 7.9-9.4 18. 9-27.l 60 50-51 Lb-94.5 85. 54.1) 15-16 133-138 50-150 50-150 40-120 175-200 2, 170 66 2 8. 59.0 32. 9-39. 8 59 52-53 98. 6-99.0 97. 1-98 6 131 -160 -160 40-140 150 2, 170 66 2 8. 8 35. 9 59 52 98.9 98. 6 16 157 75-105 -100 40-105 2, 160 66 8. 2 31. 9 5B 50 95. 5 96 1 15 144 80-110 -115 65-75 130 2, 290 66 1% 7. 5 42.0 59 52 98. 9 98. 0 15 154 60-100 60-100 50-60 110 2, 160 66 1% 6. 6 44. 0 60 52 98. 5 96. 8 17 159 -125 75-110 40-50 0 2,160 99 2 7.2 34.0 59. 51 98.4 97.4 17-18 124-150 25-85 -115 70-100 25-280 2, 160 99 2 8. 4-8. 8 33. 7-46. 7 59 50-55 98.9:99. 1 93.1-97. 1 15 156 40 50-55 15 2, 160 99 2 7. 6 32. 0 59 49 97. 7 97. 7 13-14 -150 75-120 75-125 15-115 0-200 2, 420 99 1 7.9-8. 4 39. 5-41. 8 59 47-49 99. 5-99. 7 99. 4-99. 6 12-17 129-167 60 70 20-100 0-150 2, 260 127 1 4. 4-6. 8 27. 0-33. 0 7 94. 1-96 7 94 7-96. 1

Mother liquor rate was controlled by mother liquor back pressure regulation. I

Mother liquor rate was controlled by instrument, based on the chiller outlet pressure.

634 cyrcliiig control of mother liquor was used, with maximum tlowduring the pressure stroke of the pulse piston and minimum flow during the suc n s o e. I I

'lhe mother liquor rate was placed on an "on-oi!" cycle synchronised with iston motion. Flow was "on" during the pressure stroke or the m a 116 "ct!" during the suction stroke. Back-pressure regulation was used in addition to the cyclic control. p

'could be concentrated to a purity of the order of 80 to 83 percent without the use ofthe piston. Use of the piston at a frequency of 16 cycles per minute produced some increase in purity of the para-xylene product. In-

creasing the frequency to 32 cycles per minute resulted in a further increase in purity. Further increase to 66 and to 99 cycles per minute, and a further increase to 127 cycles per minute, produced much improved results.

It will be noted that below 66 pulsations per minute, al-

though high-purity product was produced, the purity varied, Whereas at frequencies of 66 pulsations per minute and higher, high purity para-xylene was constantly and consistently produced with little variation in purity. Thus, a pulsation frequency of approximately 50 pulsa- 'tions per' minute represents a critical low frequency limit at which high-purity para-xylene can be constantly produced. However, satisfactory results are obtained at lower frequencies.

In order to illustrate some of the systems to which the invention is applicable, the following compounds are grouped with respect to their boiling points and freezing points.

B. P., C. F. P., C.

Group A:

Benzene 80 5, 5 n-Hexane 69 94 n-Heptane, 98. 52 go. 5 Carbon tetrachloride. 77 22. 8 Acrylonitrile 79 82 Ethyl alcohol 78. 5 117. 3 2,2-dlmethylpentane 79 125 3,3-dlmethylpentane 86 Methyl ethyl ketone 79. 6 86. 4 Methyl proplonate 79. 9 87. 5 Methyl acrylate--. 80. 5 1,3-cyc1ohexadiene-. 80. 5 98 2,4-dimethylpentane 80. 8 123. 4 2,2,3-trlmethy1butan 80. 9 25 Oyc1ohexane.- 81. 4 6. 5 Acetonltrile 82 42 Cyclohexene 83 -103. 7 2-methylhexane 90 --1l9 3-methylhexane .a 89. 4 119.4

Group B:

Methyl cyclohexane 100. 3 126. 3 O 010 exane neptane 2 2,4-trlmethylpentane (isooctane) biltromethane p-D1oxane 2-methyl-2-butan 2,3-dlmethylpenta 3-ethy1pentane GIOl iP oluene Methyloyclohexane 2,2,3,3-tetramethyl butane. 2,5-dlmethylhexane 2,4-dlmethy1hexane 2,3-dirnethylhexane 3,4-dimethy1hexane 3-ethyl-2-methy1pentane 3-ethy1-3-methylpentane Group D:

Aniline Toluene- 144 27. l 138. 8 47. 4 Para-xylene 138. 5 13. 2 Group G:

Ortho-cymene 175. 0 73. 5 Meta-cymene- 175. 7 -25 Para-cymene 176. 0 73. 5 Group H:

Dlrnethyl phthalate 282 5. 5 Dlmethyl isophthalate. 124 67 Dlmethyl terephthalate 140. 6 Group I:

Ortho-nltrotoluene 222. 3 04-12. g Meta-nitrotoluene 231 15. 5 Para-nltrotoluene 238 51. 3

Mixtures consisting of any combination of two or mixtures made up of components selected from different groups; for example, benzene can be'separated from a benzene-n-hexane or a benzene-n-heptane mixture in which the benzene is present in an amount greater than the eutectic concentration. In the same manner, paraxylene can be readily separated from a mixture of paraand meta-xylenes or from para-, meta-, or ortho-xylenes. Benzene can also be separated from a mixture thereof with toluene and/or aniline. Multi-component mixtures which can be effectively resolved so as to recover one or more of the components in substantially pure form include mixtures of at least two of 2,2-dimethylpentane, 2,4-dimethylpentane,'2,2,3-trimethylbutane, methyl cyclohexane, and 2,2,4-trimethylpentane, and mixtures of at least two of carbon tetrachloride, chloroform, and acetone. The invention is also applicable to the separation of individual components from a mixture of cymenes.

This invention can also be utilized to purify crude naphthalene, hydroquinone (1,4-benzenediol), paracresol, para-dichlorobenzene, and'such materials as high melting Waxes, fatty acids, and high molecular weight normal paraffins. The invention can also be used to resolve a mixture comprising anthracene, phenanthrene, and carbazole. Furthermore, the invention can be used to separate durene (1,2,4,S-tetramethylbenzene) from other C aromatics. In cases where the material to be purified has a relatively high crystallization point, the impure material is raised to a temperature at which only a portion of the mixture is in a crystalline state, and the resulting slurry is handled at such a temperature that operation is as described in connection with materials which crystallize at lower'temperatures.

The invention is also applicable to the concentration of food products. In the preparation of such concentrated foods, the process consists generally of the removal of water, in the form of ice crystals, from such products. One special class of foods which can be concentrated in this manner is that of fruit juices, such as grape, pineapple, watermelon, apple, orange, lemon, lime, tangerine, grapefruit, and the like. Beverages, such as milk, wine, beer, coffee, tea, and various liquors, can also be concentrated in such a process. The process is also applicable to theconcentration of vegetable juices.

From the foregoing, it will be seen that I have provided an improved process and apparatus in which solids, especially crystals, are moved through a crystal purification column having an intermediate filter section and a melting section with a reflux section therebetween, a varying or pulsating back-pressure being applied to the contents of the system simultaneously with the moving of the solids into said filter section. Variation and modification within the scope of the disclosure and'the claims can readily be effected by those skilled in the art. While certain process steps, examples and structures have been described for purposes of illustration, it is clear that the invention is not limited thereto.

I claim:

1. In a process in which a confined mass of crystals and adhering mother liquor are passed through a liquid removal zone, from which mother liquor is removed a reflux zone and a melt zone, in which said crystals are melted, part of the melt being withdrawn from the system and the remainder being forced countercurrently into said reflux zone to establish a reflux stream which flows from said melt zone to said liquid removal zone, the improvement which comprises forcing said reflux into said reflux zone in the form of a pulsating stream by directly applying a pulsating pressure substantially only against said melt, the pulsation of said stream occurring during sustained application of force to said crystals to feed same into said liquid removal zone.

2. The process which comprises continuously applying motive force to a confined mass of crystals with adhering liquor to move said crystals through a liquid reinoval zone, a reflux zone and a melting zone, withdrawin'g liquid from said liquid removal zone, melting said crystals in said melting zone, withdrawing part of the resulting melt from the system as a product, and forcing the remainder of said melt into said refluxzone countercurrently with respect to thefcrystals moved by the described continuous application of motive force to said crystals, said melt being thus forced in the form of a removal zone from which liquor is removed, a reflux zone and a melt zone in which said crystals are melted, part of the melt being withdrawn from the system and the remainder being forced countercurrently int'o'said reflux zone to form a reflux stream which flows from said melt zone to said liquid removal zone, the improvement which comprises forcing the remainder of said melt into said reflux zone in the form of a pulsating stream wherein the frequency of pulsation is greater than the frequency of propulsion of said crystalsthrough said liquid removal zone toward said melt zone 4. In a process in which a confined mass of-para xylene crystals and adhering liquid impurities are-passed through a liquid removal zone from which said liquid impurities are removed, a reflux zone and a m'elt'zone in which said crystals are melted, part of theflmelt being withdrawn from the system and the remainder being forced countercurrently. into said reflux zone to form a reflux stream which flows from said-melt zone to said liquid removal zone, the improvement which comprises directly applying a pulsating pressure substantially only against said melt and thus'forcing said remainder of said melt into said reflux zone in the form of a pulsating stream having a pulsation frequency of from to 200 pulsations per minute, the-pulsation of said stream occurring during sustained application of force to said crystals to feed same into said liquid removal zone. 5. A process according to claim 4 whereinthe solids content of said confined mass of crystals is in; the range to 36 weight percent.

6. A process according to claim 4 wherein the solids content of said confined mass of crystals is in theQrange to weight percent. v 1,

7. A process according to claim 4 wherein said pulsating stream has a frequency of at least 50 pulsations per minute. 1

8. A'process according to claim 4 wherein said frequency of pulsation is in the range 50 to. 165 pulsations per minute.

9. A process according to claim 8 wherein the frequency of pulsation is in the'range to pulsations per minute. 7

10. A process which compriseschilling a fruit juice to obtain a confined mass of ice crystals, passing said crystals and adhering liquor through a' filtration zone, removing liquor from said filtration zone as a product of the process, passing remaining solids through a reflux zone. in countercurrent contact with liquid produced as subsequently described, passing the crystals into a melting zone and melting said crystals, removing part of the molten material from the system, passing the remainder of said molten material to said reflux zone in a direction countercurent to the movement of said crystals to form a reflux stream which flows from said-melt zone to said filtration zone, said remainder of said molten material being supplied to said reflux zone in the form of a pulsating stream wherein pulsations are produced by directly applying a pulsating pressure substantially only against said molten material simultaneously with sustained application of force usedto feed said crystals into said filtration zone. a t I 11. A process for recovering para-xylene from a mixture comprising at least one other xylene and ethyl benzone, which process comprises cooling the mixture to obtain a solids content in the range 25 to 30 weight percent, said solids being p'reponderantly para-xylene crystals, passing the resulting mixture of crystals and liquid through a filtration zone, removing liquid from said filtration zone, passing the crystals, in the form of a confined mass of contiguous crystals with adhering mother liquor, through a reflux zone in counter-current contact with reflux liquid produced as subsequently described, passing the crystals into a melting zone and therein melting said crystals, withdrawing purified molten para-xylene as a product of the process, passing the remainder of the molten material, in the form of a pulsating stream, into said reflux zone in a direction counter-current to the movement of crystals therethrough, and directly applying a pulsating back-pressure substantially only tosaid molten material at a frequency in the range 125 to 150 pulsations per minute. I

References Cited in the file of this patent UNITED STATES PATENTS 2,540,977 Arnold Feb; 6,11951 2,598,449 Scott et a1. May 27, 1952 2,615,794 Shelby O t. 28, 1952 2,617,274 Schmidt Nov. 11,1952 2,622,114 r Carney a Dec. 16, 1952 2,683,178 I Findlay July 6 1954 2,724,508 Luther Nov. 22, 1955 UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,854,494 September 30, 1958 Rosswell W. Thomas It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line 55, after the syllable fication and before the period insert zone; columns 7 and 8, Table I, fourth column thereof, under the heading Heater section, fifth item, for 68.7 3 read 6873; same table, last column, under the headin Composite product, tenth item, for 98.9-99.5 read 98.999.3; same columns and 8, Table II, eleventh column thereof, under the heading Product, last item, for 19-7-5216 read 19.721.6; columns 9 and 10, Table III, third column thereof, under the heading Wall liquor, first item, for 2.4 read 2-4-; same table, same column, eighth item, for 5.7 read 57; columns 9 and 10, Table IV, last column thereof, under the heading Composite product, second item, for 94.7-97. read 94.797 .1; columns 11 and 12, Table VI, second column thereof, fifth item, opposite 14-15 for 18 30 read 1830; same table, sixteenth column thereof, under the heading Comp. product, opposite 9-14 for 85.5-920 read -85.592.0-; column 13, in the table, approximately line 65, for 25 read 25-; same table, third column thereof, about line 67, preceding Group H, insert M. P., C.-.

Signed and sealed this 14th day of April 1959.

Attest= KARL H. AXLINE, ROBERT C. WATSON, Attesting Ofioer. Commz'ssz'oner of Patents. 

1. IN A PROCESS IN WHICH A CONFINED MASS OF CRYSTALS AND ADHERING MOTHER LIQUOR ARE PASSED THROUGH A LIQUID REMOVAL ZONE, FROM WHICH MOTHER LIQUOR IS REMOVED A REFLUX ZONE AND A MELT ZONE, KN WHICH SAID CRYSTALS ARE MELTED, PART OF THE MELT BEING WITHDRAWN FROM THE SYSTEM AND THE REMAINDER BEING FORCED COUNTERCURRENTLY INTO SAID REFLUX ZONE TO ESTABLISH A REFLUX STREAM WHICH FLOWS FROM SAID MELT ZONE TO SAID LIQUID REMOVAL ZONE, THE IMPROVEMENT WHICH COMPRISES FORCING SAID REFLUX INTO SAID REFLUX ZONE IN THE FORM OF A PULSATING STREAM BY DIRECTLY APPLYING A PULSATING PRESSURE SUBSTANTIALLY ONLY AGAINST SAID MELT, THE PULSATION OF SAID STREAM OCCURRING DURING SUSTAINED APPLICATION OF FORCE TO SAID CRYSTALS TO FEED SAME INTO SAID LIQUID REMOVAL ZONE. 